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Journal of the University of Chemical Pl.

Kirilov and Metallurgy, 40, 3, 2005, 209-212


Technology

NON-CAKING FERTILIZERS FROM AMMONIUM NITRATE


AND SUPPLEMENTARY NUTRIENTS
Pl. Kirilov

University of Chemical Technology and Metallurgy Received 27 June 2005


8 Kl. Ohridski, 1756 Sofia, Bulgaria Accepted 25 August 2005
e-mail: ivan.gr@uctm.edu

ABSTRACT

Possibility for preparing non-caking mixed and complex fertilizers from a base fertilizer ammonium nitrate (crystal-
line and prilled) by addition of materials supplying phosphorus and potassium has been studied. Different raw materials and
different methods (dry mixing, wet mixing and drying, coating the prilled ammonium nitrate) have been applied.
A simple and easy applicable test for scoring the caking tendency of the samples was developed.
It was established the possibility to produce mixed NP fertilizer by ball blending of prilled ammonium nitrate
powdered with the studied additives and granulated triple superphosphate. So produced mixed fertilizer can be stored for
a long time without wetting and segregation.
Keywords: non-caking fertilizers, anti-caking additives, ball blending.

INTRODUCTION cal additives include the use of finely divided powders


which must cover the fertilizer uniformly such as for
Particulate ammonium nitrate is a commonly used example talc, kaolin, limestone and dolomite. Surfac-
plant fertilizer. Usually provided in nearly spherical par- tants may also be used. These additives form a hydro-
ticles referred to as prills, this fertilizer typically provides phobic film around the fertilizer granules. Other addi-
34 % mass nitrogen to the crops being fertilized. Under tives include compounds that also tend to form a hy-
cool, dry storage conditions, the product remains in good drophobic film such as paraffin wax, polyolefin wax and
physical conditions. However, under summer storage con- mineral oils.
ditions of 25-400C and 40-90% relative humidity, par- Various types of anti-caking additives are dis-
ticulate ammonium nitrate has been shown to suffer physi- closed in the following references.
cal degradation including particle breakdown into fines, An aqueous liquid anti-caking and anti-dusting
bridging and caking. Fertilizers which cake are not ame- composition for ammonium nitrate is disclosed which
nable to usual bulk storing and handling techniques and comprises from 20 to 30 parts of a sodium naphthalene
after storage cannot be applied easily in the field with sulfonate, from 17 to 28 parts of an ammonium naph-
mechanical distribution devices [1]. thalene sulfonate and from 30 to 80 parts of water. The
Several methods have been proposed to decrease composition is neutralized with an acid, like sulfuric
fertilizer caking which involve the use of additives. Typi- acid, to a pH of from about 5 to about 7 [2].

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Journal of the University of Chemical Technology and Metallurgy, 40, 3, 2005

The formation of dust or fines may be suppressed, EXPERIMENTAL


during the granulation of ammonium nitrate by a pro-
cess in which ammonium nitrate is initially granulated Materials used: triple superphosphate (TSP) -
to form a raw granulate containing fines and thereafter 44% P2O5, wet phosphoric acid (WPA) - 42% P2O5,
heated and contacted by a hydrated sulfate during a sec- Morocco phosphate (MP) - 32% P2O5, NH4NO3 (AN),
ond granulation step wherein the fines are affixed to the K2SO 4, KOH, (NH 4) 2SO 4 (AS), H 2SO 4, HNO 3 and
raw granulate [3]. NH4OH (25% NH3) - reagent grade.
A process for granulating ammonium nitrate is
developed by forming a mixture of NH4NO3, limestone Preparing of complex NK and PK fertilizers
and/or dolomite, ammonium sulphate and/or ammonium and predominant reactions between the main constitu-
phosphates and MgSO4, this later being added in any one ents in the used materials
of its crystalline forms and in various degrees of hydra-
tion, then granulating or prilling and cooling [4]. The complex NK and PK fertilizers were pre-
An improved particulate, ammonium nitrate is pared by mixing the respective materials in quantities
prepared with 2-6 % mass potassium sulfate. The po- given below in a baker, drying, grinding and sieving.
tassium sulfate suppresses crystalline phase IV III Working fraction -0.8+0.4 mm has been separated for
transitions in the ammonium nitrate particles while un- testing the cake tendency and for preparing mixed fer-
dergoing temperature variations between 18-420C. The tilizers with crystalline ammonium nitrate.
resulting fertilizer, which may be further coated to sup-
press dusting, exhibits superior resistance to caking, 1 - 100g WPA, 40g KOH, 40g H2O: (H3PO4 + KOH =
clumping and cracking [5]. KH2PO4 + H2O)
The chemical compatibility of some common fer-
tilizer materials used in bulk blends is given in [6]. The 2 - 100g WPA, 60 cm3 NH4OH: (H3PO4 + NH4OH =
only completely incompatible combination is ammo- NH4H2PO4 + H2O)
nium nitrate and urea because this mixture has a criti-
cal humidity of only 18%. Combinations of ammonium 3 - 30g TSP; 90g H2O, 5g KOH: (Ca(H2PO4)2 + 2KOH
nitrate with normal and triple superphosphates are in- = KH2PO4 + KCaPO4 + 2H2O)
compatible too. This is due to the fact that the ammo-
nium nitrate will interact with mono-calcium ortho- 4 - 30g TSP, 90g H2O, 10 cm3 NH4OH: (Ca(H2PO4)2 +
phosphate forming highly hygroscopic calcium nitrate. 2NH4OH = NH4H2PO4 + NH4CaPO4 + 2H2O)
Numerous tests have been devised to measure
the caking tendency of fertilizers. D.C. Thompson re- 5 - 20g TSP, 80g H2O, 10,3g K2SO4: (Ca(H2PO4)2 +
ported in 1972 that a literature review had revealed de- K2SO4 = 2KH2PO4 + CaSO4) presence of free H3PO4
scriptions of 41 such tests [7]. Reported accelerated cak- in TSP
ing tests differ in the equipment and conditions used to
form the fertilizer cake and the equipment used to mea- 6 - 20g TSP, 80g H2O, 10,3g K2SO4, 6,7 cm3 KOH (50%
sure cake hardness. KOH solution): (Ca(H2PO4)2 + K2SO4 = 2KH2PO4 +
From a practical point of view, the most impor- CaSO4) and (free H3PO4 + KOH = KH2PO4 + H2O)
tant fertilizers are those supplying simultaneously ni-
trogen, phosphorus and potassium to the soil. The aim 7 - 20g TSP, 80g H2O, 10,3g K2SO4, 7 cm3 NH4OH:
of the present paper is to study the possibilities of pre- (Ca(H2PO4)2 + K2SO4 = 2KH2PO4 + CaSO4) and (free
paring non-caking, more balanced (in relation to their H3PO4 + NH4OH = NH4H2PO4 + H2O)
nutrients) fertilizers from a basic fertilizer ammonium
nitrate, by addition of supplementary nutrients which 8 - 120g H2O, 30 cm3 H2SO4 (98% H2SO4 solution), 40g
contributes phosphorus and potassium, without the ad- K2SO4, 100g MP: (Ca5F(PO4)3 + 3,5H2SO4 + 1,5K2SO4
dition of a non-nutrient component. = 3KH2PO4 + 5CaSO4 + HF)

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Pl. Kirilov

Preparing of mixed fertilizers from ammonium cording to it the samples were placed into test tubes
nitrate and complex NP and PK fertilizers and were stored at ambient temperature and humidity
for a period of 5 weeks. After storage the tubes were
The samples were prepared by mixing of AN emptied to determine caking tendency. The caking ten-
(working fraction -0.8 +0.4 mm) with complex NP and dency was rated by a numerical scoring system as is
PK fertilizers (working fraction -0.8 +0.4 mm) in mass shown in Table 1.
ratio 2:1. The materials were placed into a polyethylene
tub and were shaken vigorously. Table 1. Numerical scoring system for caking tendency.

Score Condition
Preparing of complex fertilizers from ammo- 0 completely free flowing with no lumps
nium nitrate and raw materials supplying phosphorus 1 completely free flowing with lumps
2 completely set and easy flowing after light stressing on the
and potassium walls of the tube
3 completely set and flowing after moderate stressing of the
open end of the tube on hard surface
The complex NP and NPK fertilizers were pre- 4 completely set without flowing after strong stressing of the
pared by dissolution of ammonium nitrate and respec- open end of the tube on hard surface
tive raw materials in water in quantities given below,
drying, grinding and sieving. Working fraction -0.8+0.4
mm was separated for testing the caking tendency. The developed test is simple and easy for use
with very good reproducibility, possibility for storing
1- 100g WPA; 40g KOH;180g H2O; 120g AN the samples at definite conditions and especially suited
for small quantities of expensive chemicals.
2 - 100g WPA; 60 cm3 NH4OH; 50g H2O; 120g AN
RESULTS AND DISCUSSION
3 - 20g TSP; 40g H2O; 30g AN; 6 cm3 KOH (50%
KOH solution) In the first series of tests possibility for produc-
ing noncaking fertilizers containing phosphorus and
4 - 20g TSP; 40g H2O; 30g AN; 14 cm3 NH4OH potassium has been studied. The chemical composition
of the prepared samples and the data for the caking
5 - 20g TSP; 40g H2O; 30g AN; 10,3g K2SO4; 6 cm3 tendency are given in Table 2. It is seen that most of
KOH (50% KOH solution) them are non-caking. The only exception is the fertil-
izer prepared from TSP and K2SO4. Its caking rate is 2
6 - 20g TSP; 40g H2O; 30g AN; 10,3g K2SO4; 14 cm3 and it is due to the presence of free H3PO4 in the TSP.
NH4OH Every one of the prepared fertilizers has corresponding
advantages and disadvantages depending mainly from
7 - 4g K2SO4; 3,6 cm3 H2SO4 (98% H2SO4 solution); the cost of the raw materials and from the content of
15g H2O; 10g MP, 10g AN main nutrients phosphorus and potassium. For example,
KH2PO4 from WPA and KOH is high concentrated fer-
8 - 24g HNO3 (65% HNO3 solution); 20g H2O; 20g tilizer but it is very expensive. Just the opposite, KH2PO4
MP; 100g H2O; 8g K2SO4; 16,3g AS: from MP, H2SO4 and K2SO4 is very cheep but with low
Ca5F(PO4)3 + 7HNO3 + 1,5K2SO4 + 3,5(NH4)2SO4 = contents of nutrients.
3KH2PO4 + 7NH4NO3 + 5CaSO4 + HF In the second series of tests has been studied the
possibility for preparing a mixed fertilizers by labora-
Test for caking tendency tory imitation of ball blending of crystalline AN with
crystalline fertilizers, described in Table 2 in mass ra-
A simple and easy test for caking tendency of tio 2:1. From the data given in Table 3 it is seen that all
small quantities of the samples has been developed. Ac- tested mixtures are non-caking with exception of the

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Journal of the University of Chemical Technology and Metallurgy, 40, 3, 2005

Table 2. Caking tendency of preparing complex NP and Work fraction -0.8+0.4 mm was used for caking tests. In
PK fertilizers. this series an additional fertilizer was prepared by dissolu-
Raw materials Chemical composition of the samples, % Caking
tion of MP in solution of HNO3, K2SO4 and NH4SO4. AN
1 WPA + KOH
N
-
P2O5
47.0
K2 O
33.0
NPK
80.0
score
0
was not used as raw material in this experiment but it was
2
3
WPA + NH4OH
TSP + KOH
9.5
-
59.6
32.8
-
10.8
69.1
43.6
0
0
one of the products of the reaction. As can be seen from the
4
5
TSP + NH4OH
TSP + K2SO4
6.2
-
40.3
27.7
-
17.2
46.5
44.9
0
3
data given in Table 4 all the samples are non-caking.
6 TSP + K2SO4 + KOH - 26.5 23.0 49.5 0
7 TSP + K2SO4 +NH4OH 4.4 28.1 15.6 48.1 0
8 MP + H2SO4 + K2SO4 - 16.0 10.0 26.0 0 CONCLUSIONS

Table 3. Caking tendency of mixed fertilizers from am- It is shown the possibility for producing non-
monium nitrate and complex NP and PK fertilizers. caking mixed and complex fertilizers from ammonium
nitrate and complex fertilizers or raw materials, sup-
Raw materials Chemical composition of the samples, % Caking
score
plying the rest main nutrients phosphorus and potas-
N P2O5 K2 O NPK
1 AN + (WPA + KOH) 22.7 15.0 11.8 49.5 0 sium. Various methods for preparing the said fertilizers
2 AN + (WPA + NH4OH) 25.8 19.9 - 45.7 2
3 AN + (TSP + KOH) 22.7 10.9 3.6 37.2 0 are proposed. The supplementary nutrients can be ap-
4 AN + (TSP + NH4OH) 24.7 13.4 - 38.1 0
5 AN + (TSP + K2SO4 + KOH) 22.7 8.8 7.7 39.2 0 plied to ammonium nitrate by dry mixing, wet mixing
6 AN + (TSP + K2SO4 +NH4OH) 24.1 9.4 5.2 38.7 0
7 AN + (MP + H2SO4 + K2SO4) 22.7 5.3 3.3 31.3 0 and drying and by coating the prilled ammonium ni-
trate. This powdered ammonium nitrate can be used for
ball blending with granulated triple superphosphate to
Table 4. Caking tendency of complex fertilizers from
produce mixed NP fertilizer which can be stored for a
ammonium nitrate and raw materials supplying phos-
long time without any wetting and segregation.
phorus and potassium.
A simple and easy test for caking tendency of
Raw materials Chemical composition of the samples, Caking small quantities of the samples has been developed and
% score
N P2O5 K2O NPK used in this work.
1 AN + WPA + KOH 19.4 19.5 15.0 53.9 0
2 AN + WPA + NH4OH 28.1 2.3 - 30.4 0
3 AN + TSP + KOH 18.5 16.7 5.5 40.7 0
4 AN + TSP + NH4OH 19.6 17.9 - 37.5 0 REFERENCES
5 AN + TSP + K2SO4 + KOH 16.7 13.5 10.9 41.1 0
6 AN + TSP + K2SO4 +NH 4OH 20.3 13.1 8.1 41.5 0
7 AN + MP + H2SO4 + K2SO4 17.0 8.0 5.0 30.0 0
8 MP + HNO3 + K2SO4 + AS 11.4 10.7 7.1 29.2 0 1. G. Hoffmeister, Physical properties of fertilizers and
methods for measuring them, TVA, Bulletin Y-147,
mixture of AN with NH4H2PO4. Samples of prilled AN 1979, 31.
containing no conventional coating agents and additives 2. U. S. Pat. No 4717555, C05C 1/02, 1988.
were coated with powders of the prepared fertilizers 3. U. S. Pat. No 5154752, C05C 1/02, 1992.
and all of them were non-caking. So powdered prilled 4. U. S. Pat. No 5378259, C05C 1/02, 1995.
AN was mixed by ball blending with granular TSP and 5. U. S. Pat. No 5720794, C05C 1/02, 1998.
the resulting NP mixed fertilizers were stored for a long 6. G. Hoffmeister, Compatibility of Raw Materials in
time without any wetting and segregation. Blended Fertilizers, Proc. of the 12th Annual Meet
In the third series of experiments complex fertiliz- ing of the Fertilizer Industry Round Table, Wash
ers have been prepared from AN and the mentioned above ington, 1962, 8388.
raw materials. The mixing of the components has been made 7. D. C. Thompson, Fertilizer Caking and its Preven
by dissolving them in water, drying, grinding and sieving. tion, Proc. Fert. Soc., London, 125, 1972, 67.

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